Revisiting Reaction Mechanism of Regioselective Disulfide-Catalyzed Photocatalytic Aerobic Oxidative Cleavage of 1-Arylbutadienes: A Computational Study

Fıstıkçı M., LAFZİ F., EŞSİZ S.

ChemPhysChem, vol.26, no.11, 2025 (SCI-Expanded) identifier identifier

  • Publication Type: Article / Article
  • Volume: 26 Issue: 11
  • Publication Date: 2025
  • Doi Number: 10.1002/cphc.202401004
  • Journal Name: ChemPhysChem
  • Journal Indexes: Science Citation Index Expanded (SCI-EXPANDED), Scopus, PASCAL, Biotechnology Research Abstracts, Chemical Abstracts Core, Chimica, Compendex, EMBASE, INSPEC, MEDLINE
  • Keywords: aerobic oxidative cleavage, arylbutadienes, density functional theory, diaryl disulfides, DLPNO-CCSD(T)
  • Hakkari University Affiliated: Yes

Abstract

A computational study of the regioselective aerobic oxidative cleavage of 1-arylbutadienes is carried out employing density functional theory and high-level coupled-cluster methods, such as coupled-cluster singles and doubles with perturbative triples [CCSD(T)]. The results demonstrate that the reaction proceeds either via the intramolecular reduction or dimerization of peroxyl radical. These findings are in contrast to a previously proposed mechanism that progresses via formation of the dioxetane ring. The computations further indicate that the homolysis of S-S bond of diaryl disulfide derivatives cannot be achieved by irradiation with direct visible light under the reaction conditions due to the high bond dissociation energy.